Proton Exchange Membranes from Sulfonated Lignin Nanocomposites for Redox Flow Battery Applications.

Redox flow batteries (RFBs) are increasingly being considered for a wide range of energy storage applications, and such devices rely on proton exchange membranes (PEMs) to function. PEMs are high-cost, petroleum-derived polymers that often possess limited durability, variable electrochemical performance, and are linked to discharge of perfluorinated compounds. Alternative PEMs that utilize biobased materials, including lignin and sulfonated lignin (SL), low-cost byproducts of the wood pulping process, have struggled to balance electrochemical performance with dimensional stability. Herein, SL nanoparticles are demonstrated for use as a nature-derived, ion-conducting PEM material. SL nanoparticles (NanoSLs) can be synthesized for increased surface area, uniformity, and miscibility compared with macrosized lignin, improving proton conductivity. After addition of polyvinyl alcohol (PVOH) as a structural backbone, membranes with the highest NanoSL concentration demonstrated an ion exchange capacity of 1.26 meq g-1, above that of the commercial PEM Nafion 112 (0.98 meq g-1), along with a conductivity of 80.4 mS cm-1 in situ, above that of many biocomposite PEMs, and a coulombic efficiency (CE), energy efficiency (EE) and voltage efficiency (VE) of 91%, 68% and 78%, respectively at 20 mA cm-2. These nanocomposite PEMs demonstrate the potential for valorization of forest biomass waste streams for high value clean energy applications.

Utilization of chestnut shell lignin in alginate films.

BACKGROUND: Lignocellulosic structures obtained from agricultural wastes can re-design sustainable packaging materials. The present study investigated the utilization of lignocellulose (LS), alkali lignin (L) and hydroxymethylated (modified) lignin (ML), separated from chestnut shells in alginate (AL) films at 100 and 200 mg g-1 (10% and 20%, w/w based on AL), as reinforcing agents. Lignin modification and concentration effects on the AL films were characterized by water vapor permeability (WVP), as well as morphological, mechanical, optical, thermal and active properties. RESULTS: Fourier transform infrared spectroscopy results showed that extracted L and LS had different structures, and the modification of L resulted in a peak shift and a decrease in peak intensities between 1250 and 800 cm-1 . The antioxidant and antimicrobial activity tests showed that films containing L had higher activity values (P < 0.05). WVP of the films containing ML was the lowest (P < 0.05) and the results revealed that 20% (w/w) concentration had an adverse effect on the WVP of films. The addition of L, LS and ML increased the tensile strength, elastic modulus and thermal properties (P < 0.05) compared to AL control films. With an increasing concentration, films containing L-based structures showed higher opacity and relatively lower L* values (P < 0.05). CONCLUSION: These results show that the addition of lignin to biopolymers is a promising method for improving the properties of biopolymers and providing functional attributes. LS had no or little effect on the film properties; however, the modification of L had the advantage of enhancing WVP and thermal properties at the same time as showing a decrease in functional properties compared to L. © 2022 Society of Chemical Industry.

Hydrophobic, ultraviolet radiation-shielding, and antioxidant functionalities of TEMPO-oxidized cellulose nanofibril film coated with modified lignin nanoparticles.

In this study, lignin nanoparticles (LN) and octadecylamine-modified LN (LN-ODA) were utilized as coating materials to enhance the hydrophobic, antioxidant, and ultraviolet radiation-shielding (UV-shielding) properties of a TEMPO-oxidized nanocellulose film (TOCNF). The water contact angle (WCA) of the TOCNF was approximately 53° and remained stable for 1 min, while the modified LN-ODA-coated TOCNF reached over 130° and maintained approximately 85° for an hour. Pure TOCNF exhibited low antioxidant properties (4.7 %), which were significantly enhanced in TOCNF-LN (81.6 %) and modified LN-ODA (10.3 % to 27.5 %). Modified LN-ODA-coated TOCNF exhibited antioxidant properties two to six times higher than those of pure TOCNF. Modified LN-ODA exhibited thermal degradation max (Tmax) at 421 °C, while pure LN showed the main degradation temperature at approximately Tmax 330 °C. The thermal stability of TOCNF-LN-ODA-coated materials remained consistent with that of pure TOCNF, while the crystallinity index of the sample showed a slight decrease due to the amorphous nature of the lignin structure. The tensile strength of TOCNF was approximately 114.1 MPa and decreased to 80.1, 51.3, and 30.3 MPa for LN-ODA coating at 5, 10, and 15 g/m2, respectively.

Structure changes of lignin and their effects on enzymatic hydrolysis for bioethanol production: a focus on lignin modification.

Enzymatic hydrolysis contributes to obtaining fermentable sugars using pretreated lignocellulose materials for bioethanol generation. Unfortunately, the pretreatment of lignocellulose causes low substrate enzymatic hydrolysis, which is due to the structure changes of lignin to produce main phenolic by-products and non-productive cellulase adsorption. It is reported that modified lignin enhances the speed of enzymatic hydrolysis through single means to decrease the negative effects of fermentation inhibitors or non-productive cellulase adsorption. However, a suitable modified lignin should be selected to simultaneously reduce the fermentation inhibitors concentration and non-productive cellulase adsorption for saving resources and maximizing the enzymatic hydrolysis productivity. Meanwhile, the adsorption micro-mechanisms of modified lignin with fermentation inhibitors and cellulase remain elusive. In this review, different pretreatment effects toward lignin structure, and their impacts on subsequent enzymatic hydrolysis are analyzed. The main modification methods for lignin are presented. Density functional theory is used to screen suitable modification methods for the simultaneous reduction of fermentation inhibitors and non-productive cellulase adsorption. Lignin-fermentation inhibitors and lignin-cellulase interaction mechanisms are discussed using different advanced analysis techniques. This article addresses the gap in previous reviews concerning the application of modified lignin in the enhancement of bioethanol production. For the first time, based on existing studies, this work posits the hypothesis of applying theoretical simulations to screen efficient modified lignin-based adsorbents, in order to achieve a dual optimization of the detoxification and saccharification processes. We aim to improve the integrated lignocellulose transformation procedure for the effective generation of cleaner bioethanol.

Synthesis of a reactive lignin-based flame retardant and its application in phenolic foam.

To improve the flame retardancy of phenolic foam from the perspective of sustainable development, it is a feasible way to add bio-based flame retardants into phenolic foam. Lignin has a similar structure to phenol, which provides a possibility to replace part of phenol. In this paper, we prepared a kind of reactive bio-based flame retardant based on enzymatic hydrolyzed lignin, in which side chain was chemically grafted with phosphorus and nitrogen and benzene ring would participate in the phenolic condensation reaction. According to elemental analysis and ICP-OES data, the content of nitrogen and phosphorus in modified lignin (NP-L) increased to 2.95% and 3.55% respectively. Compared with original lignin, the carbon residue rate of NP-L increased from 3.25% to 12.13% because of the presence of flame retardant elements N and P. Then lignin-based flame retardant was used to replace phenol for modifying phenolic foams (NPLPFX). The limited oxygen index (LOI) and compressive strength of phenolic foam were improved effectively by adding modified lignin when the substitution rate was less than 25%. The LOI and compressive strength of the modified phenolic foam with 5% replacement amount (NPLPF5) are 55.6% and 0.24 MPa, which increased by 88% and 60% compared with pure phenolic foam. The cone calorimetric data also showed that NPLPF5 had good flame retardancy, and the peak heat release rate and total heat release were significantly lower than PF. This work suggests a novel green strategy for improving the flame retardancy performance of phenolic foam and promoting the utilization of lignin.

Multifunctional Hydrogels Based on Cellulose and Modified Lignin for Advanced Wounds Management.

Considering the complex process of wound healing, it is expected that an optimal wound dressing should be able to overcome the multiple obstacles that can be encountered in the wound healing process. An ideal dressing should be biocompatible, biodegradable and able to maintain moisture, as well as allow the removal of exudate, have antibacterial properties, protect the wound from pathogens and promote wound healing. Starting from this desideratum, we intended to design a multifunctional hydrogel that would present good biocompatibility, the ability to provide a favorable environment for wound healing, antibacterial properties, and also, the capacity to release drugs in a controlled manner. In the preparation of hydrogels, two natural polymers were used, cellulose (C) and chemically modified lignin (LE), which were chemically cross-linked in the presence of epichlorohydrin. The structural and morphological characterization of CLE hydrogels was performed by ATR-FTIR spectroscopy and scanning electron microscopy (SEM), respectively. In addition, the degree of swelling of CLE hydrogels, the incorporation/release kinetics of procaine hydrochloride (PrHy), and their cytotoxicity and antibacterial properties were investigated. The rheological characterization, mechanical properties and mucoadhesion assessment completed the study of CLE hydrogels. The obtained results show that CLE hydrogels have an increased degree of swelling compared to cellulose-based hydrogel, a better capacity to encapsulate PrHy and to control the release of the drug, as well as antibacterial properties and improved mucoadhesion. All these characteristics highlight that the addition of LE to the cellulose matrix has a positive impact on the properties of CLE hydrogels, confirming that these hydrogels can be considered as potential candidates for applications as oral wound dressings.

Cellulose-based evaporator with dual boost of water transportation and photothermal conversion for highly solar-driven evaporation.

Two-dimensional (2D) evaporation systems could significantly reduce the heat conduction loss compared with the photothermal conversion materials particles during the evaporation process. But the normal layer-by-layer self-assembly method of 2D evaporator would reduce the water transportation performance due to the highly compact channel structures. Herein, in our work, the 2D evaporator with cellulose nanofiber (CNF), Ti3C2Tx (MXene) and polydopamine modified lignin (PL) by layer-by-layer self-assembly and freeze-drying methods. The addition of PL also enhanced the light absorption and photothermal conversion performance of the evaporator due to the strong conjugation and π-π molecular interactions. After the combination process of layer-by-layer self-assembly and freeze-drying process, the as-prepared freeze-dried CNF/MXene/PL (f-CMPL) aerogel film exhibited highly interconnected porous structure with promoted hydrophilicity (enhanced water transportation performance). Benefiting these favorable properties, the f-CMPL aerogel film showed enhanced light absorption performance (surface temperature could be reached to 39 °C under 1 sun irradiation) and higher evaporation rate (1.60 kg m-2 h-1). This work opens new way to fabricate cellulose-based evaporator with highly evaporation performance for the solar steam generation and provides a new idea for improving the evaporation performance of 2D cellulose-based evaporator.

A porous carbon based on the surface and structural regulation of wasted lignin for long-cycle lithium-ion battery.

Lignin, as the second most abundant source in nature, is considered as a good precursor for hard carbon. However, direct carbonization of pure lignin leads to low surface area and porosity. Herein we develop a method to prepare lignin-based porous carbon by a self-template method assisted with surface modification. The oxygen-containing functional groups are introduced to regulate the surface chemistry of lignin. And the metal ions are chosen to coordinate with the oxygen-containing group in the lignin, which can form the carbonates to act as the self template to regulate the pores structure. The aromatic skeleton of lignin can also disperse the metal ions to bring uniform pore-forming sites. The results show that the carbonized lignin modified by chloroacetic acid (CCL) shows mesopores with surface area of 233.4384 m2 g-1. As anode for lithium-ion batteries (LIBs), the CCL shows a specific capacity of 500 mAh g-1 at 50 mA g-1. The capacity retention was 99 % after 1000 cycles at 1000 mA g-1, which are superior to most reported carbon anode. This work proposes a low-cost anode for LIBs and put forward a regulation strategy for bio-mass carbon. Besides, it would reduce the discard of lignin and alleviate the pollution.

Hydrothermal and photocatalytic synergistic pretreatment to improve the full utilization of corn stalk.

In this study, the hydrothermal and photocatalytic synergistic pretreatment for improving the full component utilization of corn stalk based on lignin first biorefining was employed to generate carbohydrates and obtain modified lignin. The results showed that the highest lignin removal ratio (40.70 %) and cellulose retention ratio (92.64 %) were obtained due to the smallest energy gap (6.05 eV) and the largest penetration distance (1.73 Å) between GVL and the lignin. And the yield of carbohydrates increased from 1.95 % to 58.17 % after hydrothermal pretreatment at 180 ℃. Furthermore, the modified lignin enhanced the flocculation effect, resulting in the increase of the removal of safranine-T by 6 times. In addition, the chemical and physical properties of modified lignin were studied and the mechanism of photocatalysis modification was explored. The research provides a new pretreatment method for the utilization of biomass and simultaneously achieves carbohydrate enrichment in bio-oil and purification of dye wastewater.

Preparation of amine-modified lignin and its applicability toward online micro-solid phase extraction of valsartan and losartan in urine samples.

In the present work, with the focus on an environmentally-friendly approach, some gels were prepared by synthesizing amine-modified lignin, extracted from sugarcane bagasse, and further esterification and subsequent freeze-drying. These lignin-based gels were implemented as extractive phases in an online micro-solid phase extraction (µSPE) setup in conjunction with high performance liquid chromatography (HPLC) with UV detector. The developed method was used for analytical determination of valsartan and losartan in urine samples. To study the effect of the functionalization process, the efficiency of the unmodified lignin and the functionalized lignin were compared both in the absence and the presence of graphene oxide (GO), presumably as a suitable doping agent. Surprisingly, higher extraction efficiency for the functionalized lignin, compared to both unmodified lignin and GO was observed. The amination process for the prepared gel was analyzed and proved by CHNS elemental analysis and Fourier transform infrared (FT-IR) spectroscopy. The morphology of sorbet was investigated via scanning electron microscope (SEM) imaging and a nanoscale cauliflower feature was observed. The method was optimized and subsequently applied to the analysis of the urine samples. Limits of detection (LOD) of 8 and 6 µg L - 1, limits of quantification (LOQ) of 27 and 20 µg L - 1 and linear dynamic range (LDR) of 27-2000 and 20-2000 µg L - 1 with intraday relative standard deviations (RSD%) of 4 and 3% were obtained for valsartan and losartan, respectively. The whole online µSPE-HPLC setup was conveniently used for the analysis of a patient urine sample and a quantity of 352 µg L - 1 of losartan was found. Acceptable relative recoveries (109-108 and 95-94% for valsartan and losartan) revealed the analytical potential of the method for the determination of drugs in complex urine samples.

Thermal, antioxidant and swelling behaviour of transparent polyvinyl (alcohol) films in presence of hydrophobic citric acid-modified lignin nanoparticles.

Lignin nanoparticles (LNP) have been esterified and etherified by citric acid and then blended with poly (vinyl alcohol) (PVA) at various loading levels (up to 10 wt%). Poly(vinyl alcohol) nanocomposite films containing unmodified and modified lignin nanoparticles (LNP and MLNP) were prepared through solvent casting approach. Microscopic investigation of films fractured surfaces confirmed that MLNP could be evenly dispersed in PVA matrix, and no macroscopic phase separation was generated in the nanocomposite films. Water contact angle, swelling efficiency and moisture adsorption properties of LNP and MLNP based films were measured and compared, revealing an overall increase of dimensional stability and reduced moisture adsorption for MLNP nanocomposites. MLNP based nanocomposite films outperformed the films containing LNP in antioxidant property and transparency, slight sacrificing in UV-absorbing, confirming these materials as promising candidates for applications requiring high antioxidant potential and improved performance towards light absorbance.